Production of qtjinone



UNITED STATES PATENT OFFICE.

JOHN H. WEISS, OF NEW YORK, N. Y., AND B. DOWNS, 01" CLIFFSIDE, NEW JERSEY, ASBIGNORS TO THE BARRETT COMPANY, A CORPORATION OF NEW JERSEY.

In Drawing.

To all whom it may concern Be it known that we, (1) JOHN M. Wmss and (2) CHARLES R. Downs, citizens of the United States, residing at (1) 210 West 110th street, and (2) Cliflside, 1n the counties of 1) New York and (2) Bergen and States of 1) New York and (2) New Jersey have inful improvevented certain new and use -ments in the Production of Quinone, of

which the followin is a specification. This invention re ates to the selective oxidatio of hydrocarbons of the benzene series or the'r derivatives, and has particular refbeen considered impossible to oxidize benzene to reduce quinone by subjecting mixtures o benzene and oxygen in the va or phase to the action of a catalyzer. It as formerly been customary, in order to roduce quinone from benzene, to first rep ace the corresponding hydro en atoms by substitution and then to oxidize the derivatives,

' or to oxidize the benzene in the liquid phase by means of an electric current.

This present invention relates to a modification of our prior process set forth in application, Serial No. 210,554, filed January 5, 1918, in that we have found that we can influence the de cc of oxidation of the benzene thereby o taining benzoquinone and maleic acid in varying proportions, or a mixture of uinone and ot er groduets such as maleic acld and formaldehy e.

Our invention ma variety of compoun s which contain a benzene ring having two CH groups in the para position, but our process will be more articularly described with reference to e zene (benzol- 0,11,) and the production of quinone therefrom.

Bpceifloation of Letters Patent.

Application fled my 27, 1818. Serial .fl'o. 286,898.

be carried out with a I PRODUCTION O1 QUINONE.

Patented Oct. 14, 1919.

A mixture of benzene and air, for example, 1s passed through a heated space in which Is contained a sultable catalyzer, such as vanadium, vanadium oxid, or other compounds containing vanadium, at such a rate, and under such conditions of temperature and pressure that there will occur a partial oxidation of benzene short of complete combustion, and even short of conversion into maleic acid or compounds of the straight chain or alipathic series as set forth in our prior application above referred to. While we have thus far obtained the most satisfactory results with vanadium oxid as the catalyzer, it is to be understood that the invention IS not restricted to the use of vanadium or its compounds, as we have succeeded in carrying out the invention and have secured satisfactory results with a. large number of other substances as catalyzers, for instance, such as molybdenum, tungsten, gold, ruthenium, cobalt and oxide of copper, manganese, cobalt, lead, chromium, antimony, cadmium and thorium.

As a specific example of carrying out our invention we may pass a mixture of oxygen and benzene, preferabl in the form 0 a vapor or spray, throug a tube containin pumice impregnated with vanadium oxi and heated between about 300 C. and 700 C. The proporations of benzene and o'xyen may vary widely and the oxygen may e pure oxygen, or oxygen in air, or the'oxygen may be mixed with diluent gases such as nitrogen or other neutral gases which may have a blanketin .efiect on the oxidation as will be more full indicated below. A certain proportion oi benzene will pass throu h unchanged. This benzene may, of course, recovered and passed through again with another quantit of oxygen for further partial oxidation. e have found that when the speed at which the mixture is assed through the heated space containin t e catalyzer is increased, a corresponding y large amount of quinone is produced within certain limits although a considerable portion of the ben zene ma iyhbe more highly oxidized to maleic acid. e process may be carried out throughout a wide range of pressure varying from a partial vacuum to a pressure far above atmospheric.

While we do not wish to confine ourselves take place, we believe, from the results which we have obtained, that the direct oxidation of benzene to maleic acid passes /K. HA.

If this theory be correct, it is evident that by controllin the extent of the oxidation the amount of t e quinone may be increased. This may be done in various ways, such, for example as by'passing the mixture of benzene and oxygen through more rapidly as already stated, or by blanketi'ng the oxygen with diluent gases, or by regulating the fineness of the pumice, or by regulatingthe tem erature, or by varyin the dimensions f the heated space throng which the benzeneand oxygen pass, etc. 0

We have found in practice that ordinarily after the mixture has passed through the treatin chamber and is condensed, there is found in the condensate some excess benzene, maleic acid, quinone, water, and other by-products. The maleic acid can be removed from the condensate in any convenient manner such ale-permitting it to crystallize or shaking the solution with water. The quinone may also be removed by any of the well known or convenient methods. For examgleaafter the maleic acid has been remove the benzene solution may be concentrated by distillation to a small volume when the guinone will crystallize out in a substantial y pure state and can be recovered and used for various purposes. Or it may be reduced to hydroqu'inone which is so widely used in photography as a dc-- veloper. 7

By varying the conditions under which this process 1s operated when using vanadium oxid as the catalyzer, various proportions of uinone to maleic acid may be obtained. f a lar r amount of quinone is reduced than is esired, or commercial conitions warrant, the excess benzene solution of the condensate containing the quinone, after the maleic acid has been removed, may be again passed through the treating chamber so that the quinone is probably further oxidized into maleic acid and some of the benzene is partially oxidized to an equal amount of quinone. We have found that quinone is not formed in constantl increasing amounts when the condense benzene and quinone from which maleic acid has been extracted is returned to the process without the extraction of quinone. Under fixed conditions for carrying out the process the following: 5

+ 200; 0! HUGE C0,

there seems to be a substantially fixed proportion of quinone to maleic acid in'the condensate, which roportion does not seem to so be materially a tered by'introducing some quinone with the benzene.

What we claim is:

1. The herein described process of treating benzene which comprises subjecting it 5 in the vapor phase to an oxygen containing gas at such a temperature and in the pres ence of such a catalyzer that benzoquinone is produced, and recovering benzoquinone from the roducts of reaction.

2. The erein described process of treating benzene which comprises subjecting it in the vapor phase to an oxygen containing gas at such a temperature and in the presence of metallic oxid as a catalyzer. so that benzoquinone is produced, and recovering benzo uinone from the products of reaction.

3. he herein described process of treating benzene which comprisessubjecting it in the vapor phase to an oxygen containing gas at such a temperature and in the presence of vanadium oxid as a catalyzer so that benzoquinone is produced, and recovering benzoquinone from the products of reaction.

4. The herein described process of treating benzene which comprises subjecting it in the vapor phase to an oxygen containing as at a temperature between 300 C. and 00 C. and in the presence of such a cata- 9o lyzer that benzoquinone is produced, and recovering benzoquinone from the products of reaction.

5. The herein described process of treating benzene which comprises subjecting it in the vapor phase to an oxygen containing as at a temperature between 300 C. and

00 C. and in the presence of metallic oxid as a catalyzer so that benzoquinone is roduced', and recovering benzoquinone mm the'products of reaction.

6. The herein described process of treat ing benzene which comprises subjecting it in the, vapor phase to an oxygen containing gas at a temperature between 300 C. and 700 C. and in the presence of vanadium oxid as a catal zer so that benzoquinone is plroduced, an recovering benzoquinone cm the products of reaction.

7. The herein described process which comprises oxidizing benzene in the vapor phase in the presence of such a catalyzer and at such a tempemture that quinone and maleic acid are produced and recovering quinone and malelc acid from the products of reaction.

8. The herein described process which comprises oxidizing benzene in the vapor phase in the presence of vanadium oxid as a catalyzer and at such a temperature that quinone and maleie acid are produced, and recovering quinone and maleic acid from the products of reaction.

9. The proces of producing quinone and maleie acid which comprises the steps of partially oxidizing benzene in the presence of vanadium oxid as a catalyzer at a temperature of about 300 C. to 700 C. condensing the resulting roducls, extracting the malcic acid from 51c condensate, eoncentrating the residue and removing the quinone therefrom.

In testimony whereof we affix our signatures.

JOHN M. WEISS. CHARLES R. DOWNS. 

